US3954489A - Method for retarding the setting time of rapid hardening cement - Google Patents

Method for retarding the setting time of rapid hardening cement Download PDF

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Publication number
US3954489A
US3954489A US05/444,650 US44465074A US3954489A US 3954489 A US3954489 A US 3954489A US 44465074 A US44465074 A US 44465074A US 3954489 A US3954489 A US 3954489A
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setting time
retarding
clinker
rapid hardening
hardening cement
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Expired - Lifetime
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US05/444,650
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English (en)
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Hiroshi Uchikawa
Hajime Kato
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Taiheiyo Cement Corp
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Onoda Cement Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators or shrinkage compensating agents
    • C04B22/0013—Boron compounds

Definitions

  • This invention relates to a method for retarding the setting time of rapid hardening cement manufactured from clinker which contains 11CaO.7Al 2 O 3 .CaX 2 (X represent a halogen atom) and solid solutions of 3CaO.SiO 2 , 2CaO.SiO 2 and 4CaO.Al 2 O 3 .Fe 2 O 3 .
  • Cement containing 11CaO.7Al 2 O 3 .CaX 2 shows instantaneous setting, and lower age strength development at short and longer periods, and therefore it had no practical use.
  • the research group of the present inventors has investigated to retard the setting time of cement prepared from the clinker and invented that (1) cement obtained by adding insoluble anhydrite to the clinker powder or intergrinding a mixture of insoluble anhydrite and the clinker in an amount such that the weight ratio of Al 2 O 3 /SO 3 in the cement is present in a range of 0.7-1.8, shows retarded setting time, (2) cement having retarded setting time, excellent workability and increased initial and longer age strengths can be obtained by adding insoluble anhydrite or a mixture of insoluble anhydrite and gypsum hemihydrate (CaSO 4 .1/2 H 2 O) to the clinker in an amount such that the weight ratio of the mixture is present in a range of 0.7-1.8 and then mixing at least one compound selected from the group consisting of sulphates, nitrates and chlorides of potassium, sodium, magnesium, calcium, aluminium and ammonium (exclusive of insoluble anhydrite and gypsum hemihydrate)
  • cement having retarded setting time can be obtained by adding insoluble anhydrite and at least one compound such as saccharides, sodium hydrogen carbonate, water soluble phosphates, aliphatic carboxylic acids, fluorosilicates, sodium silicates, lignin sulphonic acid, sulphuric acid esters of higher alcohols and alkyl sulphonate to the clinker wherein the anhydrite is present in an amount such that the weight ratio of Al 2 O 3 /SO 3 in the cement is 0.7-1.8 (U.S. application Ser. No. 253,352, now U.S. Pat. No.
  • cement having shortened setting time even at low temperature is prepared by adding at least one carbonate such as calcium carbonate, sodium carbonate, potassium carbonate and magnesium carbonate or a mixture of at least one carbonate as shown above and at least one sulphate such as calcium sulphate, sodium sulphate, potassium sulphate and magnesium sulphate to the clinker in an amount such that the weight ratio of Al 2 O 3 /SO.sub. 3 in the cement is present in a range of 0.6-1.8 (U.S. application Ser. No. 309,805, now U.S. Pat. No. 3,819,389).
  • One object of the present invention is to manufacture cement wherein the setting time thereof is retarded longer than that of cement produced from clinker containing 11CaO.7Al 2 O 3 .CaX 2 in the prior art and the high strength at short and longer periods is developed.
  • the clinker containing 11CaO.7Al 2 O 3 .CaF 2 was obtained by mixing powders of clay, bauxite, lime stone and fluorspar, intergrinding the mixture, granulating it and firing the granules in a rotary kiln at 1300°-1350°C.
  • the chemical and mineral compositions of the clinker thus obtained are shown in Table 1.
  • Insoluble anhydrite was prepared by firing phosphogypsum at 800°-900°C, grinding the fired gypsum to a specific surface area of about 8100 cm 2 /g (Blaine).
  • the chemical composition of the insoluble anhydrite thus obtained is shown in Table 2.
  • cement (sample I) was prepared by adding insoluble anhydrite to the clinker ground to the specific surface area of 5500 cm 2 /g (Blaine) in an amount such that the weight ratio of Al 2 O 3 /SO 3 in the cement was present 1.1 and cement (sample II) was prepared by adding 3 parts (weight) of calcium carbonate to 97 parts (weight) of the clinker, intergrinding the mixture to the specific surface area of 5500cm 2 /g (Blaine) and adding insoluble anhydrite to the mixture in an amount such that the weight ratio of Al 2 O 3 /SO 3 in the cement was present to 1.1.
  • boric acid were added to both cements and the setting times and compressive strengths of both cements thus obtained were tested.
  • Cement (sample III) was prepared by mixing 96 parts (wt.) of the clinker, 3 parts (wt.) of calcium carbonate and 1 part (wt.) of sodium sulphate, intergrinding the mixture to the specific surface area of 5500cm 2 /g (Blaine) and adding to the mixture insoluble anhydrite in an amount such that the weight ratio of Al 2 O 3 /SO 3 in the cement was present 1.1.
  • the setting times and compressive strengths of the mortars prepared by adding various amounts of boric acid or citric acid to the cement were tested at 5°-30°C. The results are shown in Table 3.
  • the present invention covers all methods for additionally retarding the setting time and for increasing the initial and the longer age strength of the cement which are prepared by adding insoluble anhydrite to the rapid hardening cement clinker powder of 2500-8500cm 2 /g (Blaine) containing 1-60% by weight of 11CaO.7Al 2 O 3 .CaX 2 as a mineral component in an amount such that the weight ratio of Al 2 O 3 /SO 3 in the cement is present in a range of 0.7-1.8 and by additionally adding other set-retarding agent to the above mixture of the clinker and the anhydrite.
  • the preferable added amount of at least a boric compound such as boric acid, boric acid anhydride and water soluble borate (for example, sodium borate, potassium borate and ammonium borate etc.) may be varied with the content of 11CaO.7Al 2 O 3 .CaX 2 in clinker and the temperature at which cement is hardened and generally 0.03-3% by weight based on B 2 O 3 is preferably used to the total amount of the clinker and insoluble anhydrite.
  • Addition of boric compound of less than 0.03% by weight presents only slight retarding effect, and that of over 3% by weight greatly retards the setting time but decreases the strength of the hardened specimen.
  • the setting time of the cement can be controlled widely from several minutes to 2 hours and the concrete or mortar presents exellent workability and formability and increase in its compressive strength, especially strength at early age; and therefore, the present invention has inestimable value to its industrial application.
  • cement (sample IV) was prepared by mixing 96 weight parts of the clinker in Table 1, 3 weight parts of calcium carbonate and 1 weight part of sodium sulphate and intergrinding the mixture to 5500 cm 2 /g (Blaine), and cement (sample V) was prepared by mixing 96.8 weight parts of the same clinker as the above, 3 weight parts of calcium carbonate and 0.2 weight part of sodium borate and intergrinding the mixture to 5500 cm 2 /g (Blaine), and in addition, cement (sample VI) was prepared by mixing 95.8 weight parts of the same clinker as the above, 3 weight parts of calcium carbonate, 0.8 weight part of sodium sulphate and 0.4 weight part of boric acid and intergrinding the mixture to 5500 cm 2 /g (Blaine).
  • Cement (sample VII) was prepared by mixing 85 weight parts of the clinker in Table 1 and 15 weight parts of insoluble anhydrite and intergrinding the mixture to 5500 cm 2 /g (Blaine), and in addition, cement (sample VIII) was prepared by mixing 99.4 weight parts of the above cement and 0.6 weight part of boric acid.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
US05/444,650 1973-02-21 1974-02-21 Method for retarding the setting time of rapid hardening cement Expired - Lifetime US3954489A (en)

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JA48-20266 1973-02-21
JP48020266A JPS5244335B2 (enrdf_load_html_response) 1973-02-21 1973-02-21

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US (1) US3954489A (enrdf_load_html_response)
JP (1) JPS5244335B2 (enrdf_load_html_response)
CH (1) CH592587A5 (enrdf_load_html_response)
DE (1) DE2408412B2 (enrdf_load_html_response)
FR (1) FR2218302B1 (enrdf_load_html_response)
GB (1) GB1436473A (enrdf_load_html_response)
IT (1) IT1008248B (enrdf_load_html_response)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060425A (en) * 1975-04-05 1977-11-29 Japanese National Railways Super rapid hardening mixture
US4187118A (en) * 1977-08-12 1980-02-05 Denki Kagaku Kogyo Kabushiki Kaisha Concrete composition for making concrete moldings and method for making such concrete moldings
US4210619A (en) * 1978-08-18 1980-07-01 Haley George D Cement bonded agglomerate containing boron
US4302251A (en) * 1978-11-29 1981-11-24 Denki Kagaku Kogyo Kabushiki Kaisha Cement composition containing dextrin
US4319927A (en) * 1980-05-07 1982-03-16 The Flintkote Company Portland-type cements
US4500357A (en) * 1984-04-03 1985-02-19 Halliburton Company Oil field cementing methods and compositions
US4997484A (en) * 1987-12-11 1991-03-05 Lone Star Industries, Inc. Hydraulic cement and composition employing the same
US20060289014A1 (en) * 2002-09-06 2006-12-28 Apneon, Inc. Devices, systems, and methods using magnetic force systems in or on tissue in an airway
US20070125278A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services Cement compositions comprising maltodextrin
US20070129260A1 (en) * 2005-12-01 2007-06-07 Caveny William J Additives comprising chlorinated carbohydrates
US20070125277A1 (en) * 2005-12-01 2007-06-07 Caveny William J Treatment fluids comprising chlorinated carbohydrates
US20070125539A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services Methods of Cementing Subterranean Formations Using Cement Compositions Comprising Maltodextrin
US20070129261A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services Additives Comprising Maltodextrin
US20070125538A1 (en) * 2005-12-01 2007-06-07 Caveny William J Methods of treating subterranean formations using treatment fluids comprising chlorinated carbohydrates
US20100155069A1 (en) * 2008-12-19 2010-06-24 Halliburton Energy Services, Inc. Cement Compositions Comprising Stevia Retarders
CN108358483A (zh) * 2018-04-28 2018-08-03 青海大学 一种快速提高碱式硫酸镁水泥强度和抗水性能的方法
CN110997591A (zh) * 2017-05-29 2020-04-10 拉维·康德·阿哈拉瓦特 制造水泥的方法
EP3750857A1 (en) * 2019-06-14 2020-12-16 Sika Technology Ag Method for the kinetic regulation of cementitious binders

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8300166D0 (en) * 1983-01-05 1983-02-09 Fosroc International Ltd Anchoring capsule
GB2157279A (en) * 1984-04-12 1985-10-23 Dow Chemical Co Well treating composition
US4661160A (en) * 1986-04-11 1987-04-28 The United States Of America As Represented By The Secretary Of The Navy Alkaline earth metaborates as property enhancing agents for refractory concrete
PL236821B1 (pl) 2020-01-21 2021-02-22 Politechnika Slaska Im Wincent Sposób otrzymywania warstw polimerowych na powierzchni tytanu lub stopów tytanu na bazie polimeru z tlenkami
PL236359B1 (pl) 2020-01-21 2021-01-11 Politechnika Slaska Im Wincent Sposób otrzymywania warstw polimerowych na powierzchni tytanu lub stopów tytanu
PL236823B1 (pl) 2020-01-21 2021-02-22 Politechnika Slaska Im Wincent Sposób otrzymywania warstw polimerowych na powierzchni tytanu lub stopów tytanu na bazie polimeru z fosforanami
PL237829B1 (pl) 2020-01-21 2021-05-31 Politechnika Slaska Im Wincent Sposób otrzymywania warstw polimerowych na powierzchni tytanu lub stopów tytanu na bazie polimeru z lekami

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2211368A (en) * 1939-08-18 1940-08-13 Charles H Dickens Retarder composition for cement mixtures
US2292616A (en) * 1940-01-18 1942-08-11 United States Gypsum Co Gypsum composition
US3753748A (en) * 1970-06-01 1973-08-21 Dow Chemical Co Hydraulic cement retarder composition
US3782992A (en) * 1970-12-29 1974-01-01 Onoda Cement Co Ltd Cement set retarding composition and method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA681577A (en) * 1964-03-03 M. Draganov Samuel Cement and concrete compositions
US1510795A (en) * 1921-10-29 1924-10-07 Medusa Cement Paint Company Cement paint
AT324197B (de) * 1972-03-23 1975-08-25 Perlmooser Zementwerke Ag Zement bzw. zementbeton und verfahren zu seiner herstellung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2211368A (en) * 1939-08-18 1940-08-13 Charles H Dickens Retarder composition for cement mixtures
US2292616A (en) * 1940-01-18 1942-08-11 United States Gypsum Co Gypsum composition
US3753748A (en) * 1970-06-01 1973-08-21 Dow Chemical Co Hydraulic cement retarder composition
US3782992A (en) * 1970-12-29 1974-01-01 Onoda Cement Co Ltd Cement set retarding composition and method

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060425A (en) * 1975-04-05 1977-11-29 Japanese National Railways Super rapid hardening mixture
US4187118A (en) * 1977-08-12 1980-02-05 Denki Kagaku Kogyo Kabushiki Kaisha Concrete composition for making concrete moldings and method for making such concrete moldings
US4210619A (en) * 1978-08-18 1980-07-01 Haley George D Cement bonded agglomerate containing boron
US4302251A (en) * 1978-11-29 1981-11-24 Denki Kagaku Kogyo Kabushiki Kaisha Cement composition containing dextrin
US4319927A (en) * 1980-05-07 1982-03-16 The Flintkote Company Portland-type cements
US4500357A (en) * 1984-04-03 1985-02-19 Halliburton Company Oil field cementing methods and compositions
US4997484A (en) * 1987-12-11 1991-03-05 Lone Star Industries, Inc. Hydraulic cement and composition employing the same
US20060289014A1 (en) * 2002-09-06 2006-12-28 Apneon, Inc. Devices, systems, and methods using magnetic force systems in or on tissue in an airway
US20070129261A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services Additives Comprising Maltodextrin
US7435293B2 (en) * 2005-12-01 2008-10-14 Halliburton Energy Services, Inc. Cement compositions comprising maltodextrin
US20070125277A1 (en) * 2005-12-01 2007-06-07 Caveny William J Treatment fluids comprising chlorinated carbohydrates
US20070125539A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services Methods of Cementing Subterranean Formations Using Cement Compositions Comprising Maltodextrin
US20070125278A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services Cement compositions comprising maltodextrin
US20070125538A1 (en) * 2005-12-01 2007-06-07 Caveny William J Methods of treating subterranean formations using treatment fluids comprising chlorinated carbohydrates
US7303625B2 (en) 2005-12-01 2007-12-04 Halliburton Energy Services, Inc. Treatment fluids comprising chlorinated carbohydrates
US7395861B2 (en) * 2005-12-01 2008-07-08 Halliburton Energy Services, Inc. Methods of cementing subterranean formations using cement compositions comprising maltodextrin
US7422062B2 (en) 2005-12-01 2008-09-09 Halliburton Energy Services, Inc. Methods of treating subterranean formations using treatment fluids comprising chlorinated carbohydrates
US20070129260A1 (en) * 2005-12-01 2007-06-07 Caveny William J Additives comprising chlorinated carbohydrates
US7547664B2 (en) 2005-12-01 2009-06-16 Halliburton Energy Services, Inc. Additives comprising chlorinated carbohydrates
US20100155069A1 (en) * 2008-12-19 2010-06-24 Halliburton Energy Services, Inc. Cement Compositions Comprising Stevia Retarders
US7836954B2 (en) 2008-12-19 2010-11-23 Halliburton Energy Services. Inc. Cement compositions comprising stevia retarders
CN110997591A (zh) * 2017-05-29 2020-04-10 拉维·康德·阿哈拉瓦特 制造水泥的方法
EP3630696A4 (en) * 2017-05-29 2021-02-17 Ahalawat, Ravi Kant CEMENT MANUFACTURING PROCESS
CN108358483A (zh) * 2018-04-28 2018-08-03 青海大学 一种快速提高碱式硫酸镁水泥强度和抗水性能的方法
EP3750857A1 (en) * 2019-06-14 2020-12-16 Sika Technology Ag Method for the kinetic regulation of cementitious binders
WO2020249805A1 (en) * 2019-06-14 2020-12-17 Sika Technology Ag Method for the kinetic regulation of cementitious binders
US11912631B2 (en) 2019-06-14 2024-02-27 Sika Technology Ag Method for the kinetic regulation of cementitious binders

Also Published As

Publication number Publication date
GB1436473A (en) 1976-05-19
DE2408412B2 (de) 1977-08-11
IT1008248B (it) 1976-11-10
AU6559774A (en) 1975-08-14
DE2408412A1 (de) 1974-10-17
JPS5244335B2 (enrdf_load_html_response) 1977-11-07
JPS5063013A (enrdf_load_html_response) 1975-05-29
CH592587A5 (enrdf_load_html_response) 1977-10-31
FR2218302B1 (enrdf_load_html_response) 1977-06-10
FR2218302A1 (enrdf_load_html_response) 1974-09-13

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